Use of ceramides and similar compounds in hair care compositions

ABSTRACT

A non-oxidative hair colouring composition, comprises ceramide or functionally similar related material, in the absence of phytantriol. The invention also provides a method of improving the colouring effects of non-oxidative hair colouring compositions, comprising application to the hair (during or after dyeing) of ceramide or functionally similar related material, in the absence of phytantriol. The invention also covers use of ceramide or functionally similar related material for the purpose of improving the colouring effects of a non-oxidative hair dye. The invention can be put into effect by incorporating ceramide or functionally similar related material into a hair care composition for use during non-oxidative dying of hair, where it acts to improve dye deposition onto hair, or into a composition for use on hair after dyeing by a non-oxidative method, e.g. a shampoo or conditioner composition, to help maintain the colour of dyed hair. Good results have been obtained with the ceramide materials Questamide H, Ceramide II and Questamix H.

FIELD OF THE INVENTION

This concerns hair care compositions, particularly non-oxidative haircolouring compositions, and methods of improving the colour effectsincluding the colour-fastness of non-oxidative hair colouringcompositions.

BACKGROUND TO THE INVENTION

Compositions for colouring or dyeing hair can be categorised intotemporary, semi-temporary, semi-permanent, permanent and, more recently,the so-called demi-permanent products. Although these names try todescribe the general longevity of the colour in terms of wash-out, thereis considerable blurring of the categories depending upon the brand ofhair colour purchased, the dyes used and the formulation of the carrierbase. However, as a guide:

-   -   Temporary lasts only one wash    -   Semi-temporary lasts approximately 5 washes    -   Semi-permanent lasts approximately 10 washes    -   Demi-permanent last approximately 20 washes    -   Permanent is not washed out and lasts until the colour fades or        grows out

Other products on the market are sold as post-colour formulations andthese claim to extend the life of the hair colour. These can be splitinto ‘colour maintenance’ products, normally shampoos, which areformulated to be mild and help reduce colour washout, and ‘re-tint’products, which possess a low concentration of colour to reinforce theexisting colour of the hair.

The chemistry of hair dyes differs greatly. Temporary and semi-temporarycolours tend to be larger molecules that are unable to penetrate thehair shaft and so reside on the hair surface. This makes them easy toremove with washing. Semi-permanent, demi-permanent and permanentcolours are smaller molecules, which are able to penetrate the hairshaft, making them more resistant to hair washing.

The following list is a guide to the types of dye often found in theparticular category of hair product. It should be noted that manycommercially available products contain combinations of dye types:

-   -   Temporary hair colours include food or vegetable dyes or their        insoluble lakes (pigments). Here, the colouring formulation        normally contains fixatives such as resins to hold the colour        onto the hair. These are easily removed with shampoo.    -   Semi-temporary dyes are cationic in charge. The cationic charge        allows them to bind to the hair surface and makes them more        resistant to washing.    -   Semi-permanent dyes are normally small, nitro-dyes, which are        able to penetrate the hair shaft. This makes them less readily        removed with washing.    -   Permanent dyes (and couplers) are themselves colourless        precursors called oxidation dyes. These precursors, in the        presence of peroxide, undergo a chemical reaction to produce        coloured compounds of varying degrees of polymerisation.        Penetration of the colourless precursors into the hair fibre can        be ‘encouraged’ by the use of an alkali, such as ammonia, which        causes the hair shaft to swell and become more porous. Once        within the hair fibre, the small colourless precursors        polymerize to form the larger coloured compounds. These are then        trapped within the hair fibre by their physical size.    -   Demi-permanent colours use similar, colourless, precursors to        the permanent colours. However, the use of different coupling        agents restricts polymerization to the formation of smaller        coloured compounds. These smaller compounds are more easily        washed out of the hair. Also, the reduction or elimination of        ammonia from the formulation helps to limit the penetration of        the precursors.

Many products contain a combination of different dye types. For example,some semi-temporary dyes are mixed with the semi-permanent dyes toproduce more natural looking shades. The demi-permanent and permanentproducts can provide a wide variety of colours even on dark hair becausethe natural hair colour is bleached during the process. The use of thetemporary, semi-temporary and semi-permanent colours are dependent uponthe individual's natural hair colour; a dark haired person cannot becomeblond.

The reason for the recent popularity in demi-permanent colouration comesfrom the desire to produce a more natural look and reduce damage to thehair. Demi-permanent colouring is also used to boost an old, fading,permanent colour.

Semi-temporary or semi-permanent products are used to tint the hair. Agrowing market for these colours is also in masking grey hair. This isbecause these types of colours effect the lighter (white) hairs morethan the darker hairs, helping to provide a more natural look. However,as described above, such products do not last very long.

Ceramides are a group of naturally occurring lipids present in thestratum corneum of the skin and the cuticle of the hair. The structuresof ceramides are described by Wertz P. W., Miethke M. C., Long S. A.,Strauss J. M. and Downing D. T. in ‘The composition of ceramides fromhuman stratum corneum and from comedones’, The Journal of InvestigativeDermatology, 84, 41-412 (1985). Ceramide structures have been classifiedinto 6 families known as ceramide 1 to ceramide 6 (with the ceramide 6family being sub-classified into 2 members, ceramide 6i and ceramide6ii). These families are described by Downing in Arch. Dermatol., Vol123, 1381-1384, 1987. Ceramides in each family can vary in chain lengthand unsaturation.

Ceramides are known to have beneficial effects on skin and hair, and itis known to use ceramides and functionally similar related materials(including glycoceramides, ceramide derivatives, ceramide analogues,neoceramides and so-called pseudoceramides (which are non naturallyoccurring variants of ceramides)), either naturally occurring orsynthetically produced, in skin-care and hair-care compositions.

U.S. Pat. No. 6,251,378 of L'Oreal concerns use of ceramide compounds inoxidation dyeing processes for decreasing the degradation of colour ofdyed keratin fibres, particularly human hair. Oxidation dyeing processesgenerally result in degradation of keratin fibres, and the ceramidecompounds act to protect fibres from damage during the oxidation dyeingprocess so they remain softer and less brittle (see column 2, lines 38to 42).

U.S. Pat. No. 6,110,450 of Helene Curtis concerns hair carecompositions, particularly shampoos and conditioners, including at leastone ceramide and/or glycoceramide and phytantriol, which are said toprovide hair conditioning benefits. There is incidental, passingreference to the possibility of using such compositions in conjunctionwith hair dyes (oxidation dyes and/or direct dyes) for conditioningbenefits, but no examples are included.

SUMMARY OF THE INVENTION

It has surprisingly been found that ceramides and functionally similarrelated materials have the effect of enhancing the colouring effects ofnon-oxidative dyes and also enhancing the colour-fastness of hair dyedor coloured by non-oxidative methods. This effect is neither disclosednor suggested in the prior art. Furthermore this effect is notpredictable from U.S. Pat. No. 6,251,378 as non-oxidative dyes do notdamage keratin fibres so the protective effect of ceramide compoundsdisclosed in U.S. Pat. No. 6,251,378 will not arise for non-oxidativeprocesses and compositions.

In one aspect the present invention provides a non-oxidative haircolouring composition, comprising ceramide or functionally similarrelated material, in the absence of phytantriol.

In a further aspect the invention provides a method of improving thecolouring effects of non-oxidative hair colouring compositions,comprising application to the hair (during or after dyeing) of ceramideor functionally similar related material, in the absence of phytantriol.

The invention also includes within its scope use of ceramide orfunctionally similar related material in a hair care composition for thepurpose of improving the colouring effects of a non-oxidative hair dye.

The expression “ceramide or functionally similar related material” isused to mean ceramides, glycoceramides, ceramide analogues,pseudoceramides, neoceramides and derivatives of all the foregoing. Thematerials may be naturally occurring or synthetically produced. Ingeneral terms, such materials comprise two fatty chains attached to apolar head group. Each fatty chain can vary in length from C10 to C30but will typically be between C12 and C24 and even more typicallybetween C14 and C18. The degree of saturation and/or branching of theclaims can also vary. The fatty chains may also contain one or morefunctional side groups; normally, but not exclusively, alcohol groups.The fatty chains can be acids, alcohols, amines or amides. Each fattychain can be joined to the polar head group through an ester, ether,amine or amide bond. The polar head group consists of the functionalgroups associated with the fatty chains and one or more additionalfunctional groups, normally alcohol(s), which may be further modifiedwith polyols, ethylene oxide, etc.

Suitable materials are well known to those skilled in the art and aredisclosed e.g. in U.S. Pat. No. 6,251,378, U.S. Pat. No. 6,110,450, U.S.Pat. No. 6,077,972, EP 482860, EP 97059 and WO 94/07844 and many otherdocuments. Currently preferred materials include the pseudoceramidebishydroxyethyl biscetyl malonamide (a lipid with ceramidefunctionality) as described in Example 1 of WO 94/07844 and as availablefrom Quest under the Trade Mark Questamide H; ceramide 2, particularlyin the nature-identical form obtained by synthesis and as available fromQuest under the Trade Mark Ceramide II; and a blend of lipids with thepseudoceramide bishydroxyethyl biscetyl malonamide (Questamide H) andother components found naturally in the skin and hair such as sterol,fatty acids, phospholipids and glycerine, as available from Quest underthe Trade Mark Questamix H.

Mixtures of two or more ceramides or functionally similar relatedmaterials may be used. The invention can thus be put into effect byincorporating ceramide or functionally similar related material into ahair care composition for use during non-oxidative dyeing of hair (i.e.a non-oxidative hair colouring composition) where it acts to improve dyedeposition onto hair, or into a composition for use on hair after dyeingby a non-oxidative method, e.g. a shampoo or conditioner composition, tohelp maintain the colour of dyed hair.

The invention improves the colouring effect of non-oxidative dyes by twoeffects, namely:

-   -   i) by producing improved deposition of colour onto hair when        used at the time of colouring treatment (e.g. by being        incorporated into a non-oxidative hair colouring composition);        and    -   ii) by reduced colour loss on washing of dyed hair (e.g. by        being incorporated into a shampoo), resulting in better        maintenance of colour, i.e. improving colour fastness. The        invention can thus enhance the effectiveness and the effective        life of non-oxidative hair colouring compositions.

Ceramides or functionally similar related material is suitably presentin a hair care composition in an amount in the range 0.01 to 5% byweight, preferably 0.05 to 1% by weight. Very effective results havebeen obtained with non-oxidative hair colouring compositions andshampoos containing 0.1% by weight Questamide H, with good results beingobtained with compositions containing 0.5% by weight Questamix H or0.05% by weight Ceramide II.

The hair care compositions can otherwise be of generally conventionalformulation.

The invention will be further described, by way of illustration, in thefollowing Examples.

EXAMPLE 1 Semi-Temporary Hair Colour Maintenance

Three hair swatches were coloured with the same colorant conditioner(the formula of which is given below). The three swatches weretemporarily put together to form a single tress and then wetted withwater at 45° C. Seventy grams of colour conditioner was gently massagedinto the hair tress for approximately 4 minutes, ensuring that the tresswas completely coated. The colour was then left in the hair for 15minutes before being rinsed with running water, at 45° C., until thewater ran clear (circa 3 minutes). Finally the tress was dried with ahair-dryer (with gentle combing). Conditioner formula: % w/w Propyleneglycol   17% Hydroxyethylcellulose¹  0.6% Phenonip²  0.9% Water 51.7%Arlacel 165³   5% Cetyl stearyl alcohol⁴   3% C12-15 Alkyl Benzoate⁵ 0.5% Cetearyl Isononanoate⁶  0.5% Lauryl Lactate⁷  0.5% Water   20%Colour blend  0.2% Citric acid to pH3The colour blend contains:CI 56059 is Basic Blue 99CI 12245 is Basic Red 76Ratio red/blue: 40:60¹available as Natrosol 250HHR from Aqualon/Hercules, Inc.²Phenoxyethanol (and) methylparaben (and) ethylparaben (and)propylparaben (and) butylparaben available from Nipa Labs.³Glyceryl Stearate (and) PEG-100 Stearate, available from Uniqema.⁴available as Lanette O from Cognis.⁵available as Finsolv TN from Finetex, Inc.⁶available as Cetiol SN from Cognis.⁷available as Crodamol LL from Croda Oleochemicals Limited.

The hair tress was then separated again into three swatches. Each swatchwas then cut into two parts in order to obtain six smaller hairswatches, all evenly coloured. Two swatches were kept for colourreference and labelled “initial colour”. The remaining four swatcheswere then each washed with a different shampoo containing a selectedQuest ingredient and labelled Xn (where X is the formula and n is thenumber of washes).

Four different formulae of shampoo were made: % w/w FORMULA A Sodiumlaureth sulfate⁸   35% Cocamidopropyl betaine⁹   10% Cocamide DEA¹⁰   2% Sodium chloride  2.1% Questamide H  0.1% Water  50.8% FORMULA BSodium laureth sulfate⁸   35% Cocamidopropyl betaine⁹   10% CocamideDEA¹⁰    2% Sodium chloride  2.1% Water  50.9% FORMULA C Sodium laurethsulfate⁸   35% Cocamidopropyl betaine⁹   10% Cocamide DEA¹⁰    2% Sodiumchloride  2.1% Questamix H  0.5% Water  50.4% FORMULA D Sodium laurethsulfate⁸   35% Cocamidopropyl betaine⁹   10% Cocamide DEA¹⁰    2% Sodiumchloride  2.1% Ceramide II  0.05% Water 50.85%⁸available as Texapon NSO/IS from Cognis.⁹available as Tegobetain F50 from Th Goldschmidt AG.¹⁰available as Empilan CDE from Cognis.

The four hair swatches were each washed seven times following a preciseprotocol, with each swatch being shampooed in a different shampoo (A, B,C or D). The swatches were firstly wetted with water at 45° C. Eachswatch was ‘coated’ in 10 grams of the relevant shampoo and then, whilstbeing supported in one hand, rubbed with the fingers in a way that bestreproduces the action of washing the hair in vivo. The hair was rinsedclean with running water at 45° C. before being dried with a hair dryer(with gentle combing).

Using a Minolta Colorimeter, the base hair swatch colour was measuredprior to application of the colour, after the hair had been coloured,and after the final (seventh) wash and dry regime. The freshly colouredswatches and the final washed/dried swatches were also visually comparedand ranked (blind) for colour intensity, using an untrained panel ofvolunteers.

The Minolta Colorimeter measures three aspects of colour:

-   -   L is the luminosity (0 black and 100 very bright)    -   a is a green-red scale (negative is green and positive is red)    -   b is a blue-yellow scale (negative is blue and positive is        yellow)        Colorimeter Results

Hair Swatch Colour Before Colouring: {circle over (1)} L 78.62 {circleover (2)} L 79.23 {circle over (3)} L 78.60 mean L 78.82 a +2.71 a +1.89a +2.14 a +2.25 b +20.79 b +20.08 b +20.40 b +20.42

“Initial Colour” Swatches (not washed): {circle over (1)} L 25.25{circle over (2)} L 28.82 {circle over (3)} L 30.41 mean L 28.16 a+12.34 a +13.31 a +13.23 a +12.96 b −0.69 b −1.45 b −0.50 b −0.88

Xn Swatches After Seven Washes: SWATCH SWATCH SWATCH SWATCH A₇ B₇ C₇ D₇Measure 1 L 45.83 L 51.11 L 49.62 L 47.20 a +9.36 a +9.37 a 8.90 a+10.38 b +2.11 b +2.29 b +3.42 b +1.62 Measure 2 L 50.39 L 52.58 L 52.44L 48.52 a +7.66 a +7.91 a +8.43 a +9.93 b +3.41 b +2.95 b +3.16 b +2.75Measure 3 L 50.10 L 55.98 L 51.14 L 54.08 a +9.18 a +7.53 a +9.97 a+7.68 b +3.02 b 4.07 b +3.50 b +3.24 Mean L 48.78 L 53.22 L 51.06 L49.93 a +8.73 a +8.27 a +9.1 a +9.33 b +2.85 b +3.10 b +3.36 b +2.53

The colour difference between the freshly coloured hair and the finalwashed/dried hair (final hair colour-initial hair colour) can becalculated from the Minolta Colorimeter measurements. This gives Δ L, Δa and Δ b for each formulation. It should be noted that a smaller Δ Lvalue represents a darker hair swatch (more hair colour), a morenegative Δ a value represents less red (less hair colour), and a morepositive Δ b value represents less blue (less hair colour): Δ L Δ a Δ bQuestamide H (formula A) +20.62 −4.23 +3.73 Questamix H (formula C)+22.90 −3.86 +4.24 Ceramide II (formula D) +21.77 −3.63 +3.41 Withoutingredient (formula B) +25.06 −4.69 +3.98

Visual Assessment (Ranking) After 7 washes Stronger colour Less colouredVolunteer 1 A D C B Volunteer 2 A D C B Volunteer 3 D A C B Volunteer 4A C D B Volunteer 5 A D C BAnalysis of Data

The Δ L, Δ a and Δ b values show that the best colour retention wasobtained with Questamide H, followed by Ceramide II/Questamix H. Thebase shampoo performed the worst.

Visual assessment (ranking) of the colour of the hair swatches confirmedthat the Questamide H containing shampoo provided the best colourretention. Next came Ceramide II, then Questamix H and, lastly, the baseshampoo.

Conclusion

The base shampoo, which was formulated using the actives found in mostshampoos on the market, was shown to cause a high loss of temporary haircolour over the seven washes. Incorporation of the Quest ceramideingredients into the shampoo base reduced the amount of colour lost.

EXAMPLE 2 Semi-Temporary Hair Colour Deposition and Maintenance

Four hair swatches, each 21 cm long and weighing 13 grams, were colouredwith different formulae containing selected Quest ingredients followinga precise protocol: % w/w FORMULA E Propylene glycol   17% Natrosol250HHR  0.6% Phenonip  0.9% Water  51.7% Arlacel 165    5% Cetyl stearylalcohol    3% Finsolv TN  0.5% Cetiol SN  0.5% Crodamol LL  0.5%Questamide H  0.1% Water   20% Colour blend  0.2% Citric acid to pH3FORMULA F Propylene glycol   17% Natrosol 250HHR  0.6% Phenonip  0.9%Water  51.8% Arlacel 165    5% Cetyl stearyl alcohol    3% Finsolv TN 0.5% Cetiol SN  0.5% Crodamol LL  0.5% Water   20% Colour blend  0.2%Citric acid to pH3 FORMULA G Propylene glycol   17% Natrosol 250HHR 0.6% Phenonip  0.9% Water  51.3% Arlacel 165    5% Cetyl stearylalcohol    3% Finsolv TN  0.5% Cetiol SN  0.5% Crodamol LL  0.5%Questamix H  0.5% Water   20% Colour blend  0.2% Citric acid to pH3FORMULA H Propylene glycol   17% Natrosol 250HHR  0.6% Phenonip  0.9%Water 51.75% Arlacel 165    5% Cetyl stearyl alcohol    3% Finsolv TN 0.5% Cetiol SN  0.5% Crodamol LL  0.5% Ceramide II  0.05% Water   20%Colour blend  0.2% Citric acid to pH3

The colour blend contains:

-   -   CI 56059 is Basic Blue 99 and    -   CI 12245 is Basic Red 76

Ratio red/blue: 40:60

The hair swatches were first wetted with water at 45° C. Thirty grams ofeach colour conditioner formula was applied to a single wetted hairswatch and massaged gently into the hair for 3 minutes using a glovedhand. These colour conditioners were then left on the hair for 15minutes before being rinsed with running water, at 45° C., until thewater ran clear (circa 2 minutes). Finally the swatches were dried usinga 500 Watt hair-dryer with gentle combing.

Washing

Each coloured hair swatch was cut into 2 equal parts: one to keep as theoriginal colour (labelled X₀ where X is the formula reference) and theother to test the colour resistance to repeated shampooing (labelledX_(n) where X is the formula reference and n represents the number ofwashes). The swatches were each washed seven times following a preciseprotocol. The swatches were firstly wetted with water at 45° C. Eachswatch was ‘coated’ in 10 grams of shampoo formula below and then,whilst being supported in one hand, rubbed with the fingers in a waythat best reproduces the action of washing the hair in vivo. Theswatches were rinsed clean with running water at 45° C. before beingdried with a hair dryer (with gentle combing).

Shampoo formula used for the test: % w/w Sodium laureth (2) sulfate(28%) 12.00 Cocamidopropyl betaine (28%) 10.00 Cocamide DEA 2.00 Sodiumchloride 2.10 Preservative 0.10 Water 73.80Colour Analysis

Using a Minolta Colorimeter, the base hair swatch colour was measuredprior to application of the colour, after the hair had been coloured,and after each washing/drying regime. The freshly coloured swatches andthe final washed/dried swatches were also visually compared and ranked(blind) for colour intensity, using an untrained panel of volunteers.

Results

Colorimeter Measurements

Hair Swatch Colour before colouring: {circle over (1)} L 78.62 {circleover (2)} L 79.23 {circle over (3)} L 78.60 mean L 78.82 a +2.71 a +1.89a +2.14 a +2.25 b +20.79 b +20.08 b +20.40 b +20.42

After colouring (not washed): SWATCH SWATCH SWATCH SWATCH E₀ F₀ G₀ H₀Measure 1 L 27.81 L 26.77 L 31.68 L 27.02 a +12.92 a +12.58 a +13.71 a+12.14 b −1.62 b −0.23 b −1.33 b −1.32 Measure 2 L 27.13 L 31.13 L 29.73L 28.74 a +12.09 a +14.25 a +13.87 a +12.06 b −1.69 b −1.13 b −1.55 b−1.78 Measure 3 L 28.18 L 29.89 L 30.74 L 29.10 a +12.24 a +13.34 a+12.79 a +12.90 b −1.81 b −0.60 b −0.81 b −1.78 Mean L 27.70 L 29.3 L30.72 L 28.3 a +12.42 a +13.4 a +13.45 a +12.4 b −1.70 b −0.65 b −1.23 b−1.6

After the first wash: SWATCH SWATCH SWATCH SWATCH E₁ F₁ G₁ H₁ Measure 1L 35.89 L 40.11 L 34.28 L 34.93 a +12.15 a +12.35 a +13.20 a +12.82 b−1.57 b +1.49 b −1.28 b −2.46 Measure 2 L 37.22 L 34.19 L 35.37 L 32.29a +11.99 a +13.17 a +12.77 a +13.14 b −0.99 b −0.51 b −0.96 b −1.86Measure 3 L 32.89 L 32.12 L 36.84 L 34.07 a +12.85 a +12.54 a +12.43 a+13.18 b −1.79 b −0.62 b −0.65 b −1.75 Mean L 35.33 L 35.47 L 35.50 L33.76 a +12.33 a +12.72 a +12.81 a +13.05 b −1.45 b +0.12 b −0.96 b−2.02

After the second wash: SWATCH SWATCH SWATCH SWATCH E₂ F₂ G₂ H₂ Measure 1L 43.79 L 38.93 L 38.25 L 38.54 a +10.84 a +12.24 a +13.97 a +12.44 b−0.34 b +0.24 b −0.56 b −0.95 Measure 2 L 35.44 L 38.85 L 41.77 L 41.69a +13.35 a +11.80 a +12.63 a +11.39 b −2.15 b +0.37 b +0.52 b −0.39Measure 3 L 39.19 L 43.77 L 40.67 L 38.03 a +13.67 a +11.40 a +13.29 a+13.50 b −1.55 b +1.22 b −0.58 b −1.54 Mean L 39.47 L 40.51 L 40.23 L39.42 a +12.62 a +11.81 a +13.29 a +12.44 b −1.35 b +0.61 b −0.21 b−0.94

After the third wash: SWATCH SWATCH SWATCH SWATCH E₃ F₃ G₃ H₃ Measure 1L 37.89 L 42.86 L 42.00 L 42.15 a +12.77 a +12.80 a +12.58 a +12.51 b−1.20 b −0.55 b −0.85 b −0.85 Measure 2 L 42.32 L 42.04 L 42.74 L 40.32a +12.77 a +13.26 a +13.22 a +13.16 b −1.35 b −0.69 b −0.72 b −0.79Measure 3 L 39.81 L 42.22 L 43.07 L 41.93 a +13.36 a +13.29 a +13.30 a+12.40 b −1.84 b +0.32 b −0.93 b −1.09 Mean L 40.00 L 42.37 L 42.60 L41.46 a +12.97 a +13.12 a +13.03 a +12.69 b −1.46 b −0.31 b −0.83 b−0.91

After the fourth wash: SWATCH SWATCH SWATCH SWATCH E₄ F₄ G₄ H₄ Measure 1L 43.50 L 46.87 L 46.51 L 43.50 a +12.46 a +11.76 a +12.58 a +12.39 b−0.98 b +0.95 b +1.19 b +0.06 Measure 2 L 42.80 L 45.40 L 43.33 L 45.91a +13.13 a +12.57 a +13.52 a +11.22 b −0.92 b +0.84 b −0.61 b +0.17Measure 3 L 43.30 L 47.00 L 47.20 L 44.49 a +13.00 a +11.66 a +11.90 a+11.87 b −0.17 b +0.90 b +1.07 b +0.21 Mean L 43.2 L 46.42 L 45.68 L44.63 a +12.86 a +11.99 a +12.66 a +11.83 b −0.69 b +0.90 b +0.55 b+0.15

After the fifth wash: SWATCH SWATCH SWATCH SWATCH E₅ F₅ G₅ H₅ Measure 1L 41.73 L 50.56 L 48.06 L 46.61 a +12.25 a +9.96 a +11.19 a +10.37 b−0.92 b +2.32 b +0.86 b +0.36 Measure 2 L 46.83 L 45.47 L 47.71 L 46.43a +11.04 a +11.84 a +10.79 a +10.95 b +0.61 b +1.71 b +0.61 b +0.85Measure 3 L 46.96 L 51.84 L 46.60 L 46.06 a +10.83 a +9.97 a +11.35 a+10.45 b +0.45 b +3.17 b +0.88 b +1.62 Mean L 45.17 L 49.29 L 47.46 L46.37 a +11.37 a +10.59 a +11.11 a +10.59 b +0.05 b +2.40 b +0.78 b+0.94

After the sixth wash: SWATCH SWATCH SWATCH SWATCH E₆ F₆ G₆ H₆ Measure 1L 46.71 L 52.21 L 49.52 L 51.24 a +10.80 a +9.40 a +9.96 a +8.34 b +0.40b +3.40 b +1.84 b +2.46 Measure 2 L 46.20 L 53.14 L 48.76 L 45.50 a+10.85 a +8.74 a +10.20 a +9.65 b −0.43 b +3.40 b +1.40 b +0.75 Measure3 L 46.72 L 53.82 L 51.53 L 50.61 a +10.76 a +8.94 a +9.73 a +8.47 b+0.32 b +3.77 b +2.26 b +2.52 Mean L 46.54 L 53.05 L 49.94 L 49.12 a+10.80 a +9.03 a +9.96 a +8.82 b +0.09 b +3.52 b +1.83 b +1.91

After the seventh wash: SWATCH SWATCH SWATCH SWATCH E₇ F₇ G₇ H₇ Measure1 L 48.94 L 52.54 L 52.74 L 49.84 a +10.10 a +9.14 a +9.70 a +10.77 b+0.68 b +3.36 b +2.77 b +0.64 Measure 2 L 47.67 L 52.46 L 51.32 L 54.00a +10.94 a +9.15 a +10.69 a +8.55 b +1.06 b +3.01 b +3.58 b +2.91Measure 3 L 55.20 L 55.38 L 50.87 L 52.55 a +8.16 a +9.04 a +10.53 a+9.35 b +3.31 b +4.52 b +2.70 b +2.23 Mean L 50.60 L 54.1 L 51.64 L52.13 a +9.73 a +9.11 a +10.31 a +9.56 b +1.68 b +3.63 b +3.02 b +1.93

The colour difference between the freshly coloured hair and the finalwashed/dried hair (final hair colour-initial hair colour) can becalculated from the Minolta Colorimeter measurements. This gives Δ L, Δa and Δ b for each formulation. It should be noted that a smaller Δ Lvalue represents a darker hair swatch (more hair colour), a morenegative Δ a value represents less red (less hair colour), and a morepositive Δ b value represents less blue (less hair colour): Δ L Δ a Δ bQuestamide H (formula E) +22.9 −2.69 +3.38 Questamix H (formula G)+20.92 −3.14 +4.25 Ceramide II (formula H) +23.83 −2.84 +3.53 Withoutingredient (formula F) +24.8 −4.29 +4.28

Visual Assessment (Ranking) Stronger colour Less coloured Aftercolouring Volunteer 1 E H G F Volunteer 2 G E H F Volunteer 3 E H G FVolunteer 4 E H G F Volunteer 5 E G H F Volunteer 6 E H G F Volunteer 7G E H F After 7 washes Volunteer 1 E H G F Volunteer 2 G E H F Volunteer3 E G H F Volunteer 4 E H G F Volunteer 5 E H G F Volunteer 6 E G H FVolunteer 7 E G H FAnalysis of DataHair Colour Prior to Washing

Comparison of the mean ‘L’, ‘a’ and ‘b’ values of the swatches, prior towashing, shows that the best colour deposition was obtained with theQuestamide H containing formulation, followed by Ceramide II and/orQuestamix H, and finally the base colour conditioner. The visual rankingof the hair swatches confirms this result, with hair swatches treatedwith Questamide H, Ceramide II or Questamix H showing a stronger colourintensity compared to the base conditioner treated swatch being chosenunanimously as the poorest.

Hair Colour After Washing Seven Times

The Δ L, Δ a and Δ b values show the same ranking as that observed priorto washing. Visually, it becomes even clearer that Questamide H producesthe strongest hair colouring, followed by Questamix H/Ceramide II, andthen, finally, the base conditioner.

Conclusion

The use of the Quest lipids at the above concentrations, particularlyQuestamide H, produces a stronger colour deposition than the base colourconditioner alone. This effect is maintained following repeated washingwith shampoo.

EXAMPLE 3 Semi-Permanent Hair Colour Deposition

Four hair swatches, each 21 cm long and weighing 13 grams, were colouredwith different formulae containing selected Quest ingredients followinga precise protocol: % w/w FORMULA I Propylene glycol  10% Natrosol250HHR 1.5% Phenonip 0.5% Water 84.15%  Plantacare 2000 UP¹ 0.25%  Cetylalcohol 1.5% Ceteareth-20² 1.5% Questamide H 0.1% Colour Base  10%FORMULA J Propylene glycol  10% Natrosol 250HHR 1.5% Phenonip 0.5% Water84.25%  Plantacare 2000 UP¹ 0.25%  Cetyl alcohol 1.5% Ceteareth-20² 1.5%Colour Base  10% FORMULA K Propylene glycol  10% Natrosol 250HHR 1.5%Phenonip 0.5% Water 83.75%  Plantacare 2000 UP¹ 0.25%  Cetyl alcohol1.5% Ceteareth-20² 1.5% Questamix H 0.5% Colour Base  10% FORMULA LPropylene glycol  10% Natrosol 250HHR 1.5% Phenonip 0.5% Water 84.2% Plantacare 2000 UP¹ 0.25%  Cetyl alcohol 1.5% Ceteareth-20² 1.5%Ceramide II 0.05%  Colour Base  10% The colour base contains:Ethoxydiglycol 5.5% Water 4.2% 3-Nitro-p-hydroxyethylaminophenol 0.3%¹Sodium Laureth Sulphate (and) Lauryl Glucoside¹ available from Cognis.²available as Eumulgin B2 from Cognis.

Preparation of the conditioners was carried out by mixing all theingredients and heating to 80° C. Once the solution had reached thedesired temperature it was mixed under high shear. The solution was thencooled with continuous slow stirring. Finally 5 grams of the colour basewas added to 45 grams of each of the base formulations.

The hair swatches were first wetted with water at 45° C. Thirty grams ofeach colour conditioner formula was applied to a single wetted hairswatch and massaged gently into the hair for 3 minutes using a glovedhand. The colour conditioners were left on the hair for 27 minutesbefore being rinsed with running water, at 45° C., until the water ranclear (circa 2 minutes). Finally the hair swatches were dried using a500-watt hair-dryer with gentle combing.

Colour Analysis

Using a Minolta Colorimeter, the base hair swatch colour was measuredprior to application of the colour and after the hair had been coloured.The freshly coloured swatches were also visually compared and ranked(blind) for colour intensity, using an untrained panel of volunteers.

Results

Colorimeter Measurements

Before colouring: {circle over (1)} L 80.06 {circle over (2)} L 78.98{circle over (3)} L 79.12 mean L 79.39 a +0.59 a +1.90 a +2.10 a +1.53 b+17.74 b +20.22 b +20.94 b +19.63

After colouring SWATCH SWATCH SWATCH SWATCH I₀ J₀ K₀ L₀ Measure 1 L51.12 L 62.06 L 57.13 L 58.11 a +38.61 a +28.11 a +33.65 a +30.89 b+32.99 b +28.22 b +30.58 b +29.27 Measure 2 L 50.05 L 60.33 L 55.41 L57.94 a +41.20 a +31.70 a +35.33 a +32.41 b +34.69 b +29.65 b +31.94 b+30.23 Measure 3 L 48.78 L 56.76 L 52.67 L 56.23 a +44.35 a +35.49 a+39.17 a +34.50 b +36.31 b +32.17 b +34.38 b +31.06 Mean L 49.98 L 59.72L 55.07 L 57.43 a +41.39 a +31.77 a +36.05 a +32.60 b +34.66 b +30.01 b+32.30 b +30.19

Visual Assessment (Ranking) After colouring Stronger colour Lesscoloured Volunteer 1 I K L J Volunteer 2 I K L J Volunteer 3 I K J LVolunteer 4 I K L J Volunteer 5 I K L J Volunteer 6 I K L JAnalysis of Data

Comparison of the mean ‘L’, ‘a’ and ‘b’ values of the swatches, showsthat the best colour deposition was obtained with the Questamide Hcontaining formulation, followed by Questamix H, then Ceramide II andfinally the base colour conditioner. The visual ranking of the hairswatches confirms this result with hair swatches treated with QuestamideH, Questamix H showing a stronger colour intensity whilst the baseconditioner treated hair was chosen almost unanimously as the poorest.

Conclusion

The use of the Quest ingredients at the above concentrations produces astronger colour deposition than the base colour conditioner alone. Inparticular, Questamide H produces a strong colour deposition that iseasily detected by untrained volunteers.

1. A non-oxidative hair colouring composition, comprising ceramide orfunctionally similar related material, in the absence of phytantriol. 2.A composition according to claim 1, comprising ceramide or functionallysimilar related material in an amount in the range 0.01 to 5% by weight.3. A composition according to claim 2, comprising ceramide orfunctionally similar related material in an amount in the range 0.05 to1% by weight.
 4. A method of improving the colouring effects ofnon-oxidative hair colouring compositions, comprising application to thehair of ceramide or functionally similar related material, in theabsence of phytantriol.
 5. The method which comprises including ceramideor functionally similar related material in a hair care composition forthe purpose of improving the colouring effects of a non-oxidative hairdye.
 6. The composition or method according to any one of claims 1-5,wherein the ceramide or functionally similar related material comprisesone or more ceramides or pseudoceramides.
 7. The composition or methodaccording to claim 6, wherein the ceramide comprises ceramide
 2. 8. Thecomposition or method according to claim 6, wherein the pseudoceramidecomprises bishydroxyethyl biscetyl malonamide.
 9. A method of improvingthe colouring effects of a non-oxidative hair dye which comprisesapplying to hair, ceramide or pseudoceramide before, during or afterapplication of the hair dye to said hair.